WO2012028882A1 - An adhesion promoting compound - Google Patents
An adhesion promoting compound Download PDFInfo
- Publication number
- WO2012028882A1 WO2012028882A1 PCT/GB2011/051641 GB2011051641W WO2012028882A1 WO 2012028882 A1 WO2012028882 A1 WO 2012028882A1 GB 2011051641 W GB2011051641 W GB 2011051641W WO 2012028882 A1 WO2012028882 A1 WO 2012028882A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ink
- coating
- polyamide
- adhesion
- adhesion promoter
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- 230000001737 promoting effect Effects 0.000 title description 5
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 90
- 238000000576 coating method Methods 0.000 claims abstract description 85
- 239000000758 substrate Substances 0.000 claims abstract description 69
- 239000011248 coating agent Substances 0.000 claims abstract description 60
- 239000004952 Polyamide Substances 0.000 claims abstract description 55
- 229920002647 polyamide Polymers 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000009459 flexible packaging Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 39
- 238000003475 lamination Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 150000001412 amines Chemical class 0.000 claims description 26
- -1 titanium orthoester Chemical class 0.000 claims description 23
- 239000000654 additive Substances 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 229920006122 polyamide resin Polymers 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000013522 chelant Substances 0.000 claims description 6
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008199 coating composition Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229930194542 Keto Natural products 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000000976 ink Substances 0.000 abstract description 146
- 239000007788 liquid Substances 0.000 abstract description 23
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 32
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 238000009472 formulation Methods 0.000 description 17
- 238000007639 printing Methods 0.000 description 16
- 238000004383 yellowing Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 238000002845 discoloration Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000020 Nitrocellulose Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 229920001220 nitrocellulos Polymers 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000003854 Surface Print Methods 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- CNLVKRYETIVYNZ-UHFFFAOYSA-J butyl phosphate;titanium(4+) Chemical compound [Ti+4].CCCCOP([O-])([O-])=O.CCCCOP([O-])([O-])=O CNLVKRYETIVYNZ-UHFFFAOYSA-J 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- TVCBSVKTTHLKQC-UHFFFAOYSA-M propanoate;zirconium(4+) Chemical compound [Zr+4].CCC([O-])=O TVCBSVKTTHLKQC-UHFFFAOYSA-M 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- IAGCDJZAYOZMCS-UHFFFAOYSA-N 2-hydroxypropanoic acid;titanium Chemical compound [Ti].CC(O)C(O)=O IAGCDJZAYOZMCS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000007774 anilox coating Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229920002457 flexible plastic Polymers 0.000 description 2
- 238000007647 flexography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- RIPZIAOLXVVULW-UHFFFAOYSA-N pentane-2,4-dione Chemical compound CC(=O)CC(C)=O.CC(=O)CC(C)=O RIPZIAOLXVVULW-UHFFFAOYSA-N 0.000 description 2
- NVTPMUHPCAUGCB-UHFFFAOYSA-N pentyl dihydrogen phosphate Chemical compound CCCCCOP(O)(O)=O NVTPMUHPCAUGCB-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- XHMWPVBQGARKQM-UHFFFAOYSA-N 3-ethoxy-1-propanol Chemical compound CCOCCCO XHMWPVBQGARKQM-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 229910017107 AlOx Inorganic materials 0.000 description 1
- 101100518161 Arabidopsis thaliana DIN4 gene Proteins 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- PCIGTTWKYUNLEP-UHFFFAOYSA-N azane;2-hydroxypropanoic acid;titanium;dihydrate Chemical compound N.N.O.O.[Ti].CC(O)C(O)=O.CC(O)C(O)=O PCIGTTWKYUNLEP-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 210000004905 finger nail Anatomy 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24851—Intermediate layer is discontinuous or differential
Definitions
- Adhesion promoters have long been used in liquid inks to improve adhesion and resistance properties to enable the liquid ink formulations to meet the requirements of the customer and the end-user.
- the main purposes of the adhesion promoter is to improve adhesion to prevent removal of ink from the substrate and to prevent potential contamination of the packaged product due to ink removal.
- Titanium based compounds are widely used in liquid inks to improve the adhesion of the color system to substrates such as flexible packaging.
- Adhesion promoters to date produce the desired properties after a specified dwell time, for example 24 hours or longer, and impart limited adhesion to some substrates, especially those with low surface tension and coated substrates, for example those coated with aluminum oxide and silica oxide.
- Those titanium based compounds may be used without a synergist, as described for example in US4094853, US4087402, US4659848, WO04053003 and US7619021, or with a synergist, as disclosed in US4725501, US4909846 and US5116411.
- Adhesion promoters currently employed in liquid inks for flexible packaging typically have the following characteristics and performance properties:
- odor issues for example odor associated with the release of acetyl acetone (2,4-pentanedione) present in titanium acetyl acetone adhesion promoters; the release of propionic acid when using zirconium propionate adhesion promoter and the release of amylic alcohol.
- Require additional resins such as but not limited to high acid value additives, (i.e. greater than 100mg/KOH), to minimize and/or control thickening in the ink or coating medium.
- high acid value additives i.e. greater than 100mg/KOH
- ink removal or transfer may be viewed as a mode of failure.
- WO 2005/049662 discloses an adhesion-modified acid functional polyamide resin including a non-yellowing titanate chelate having amyl acid phosphate ligands. Due to the potential for amyl acid phosphate to breakdown to amylic alcohol, the adhesion modifier in WO 2005/049662 can create an odor.
- hydroxy- functional resins for example nitrocellulose, polyvinyl butyral, cellulose acetate butyrate, polyamide, polyurethane, etc.
- WO 2004/053003 describes the general mechanism of adhesion as occurring via a condensation reaction between titanium alkoxy groups and polymer hydroxyls.
- WO 2004/053003 also explains that the mechanism of thickening in the ink is due to a tendency for a crosslinking reaction to occur in the coating formulation during storage or during mixing.
- liquid inks have traditionally employed the use of high acid value materials, for example, maleic resin, dodecyl benzene sulphonic acid, ortho- phosphoric acid, dimerised rosin, etc., with an acid value in excess of 25 mg KOH/g and more preferably in excess of 100 mg KOH/g to reduce the undesirable thickening during storage. Thickening is determined by measuring the viscosity of the ink at the time of the final quality control check after manufacture and comparing this to the viscosity at a later time, for example after a period of 24 hours, several days, months or even years.
- high acid value materials for example, maleic resin, dodecyl benzene sulphonic acid, ortho- phosphoric acid, dimerised rosin, etc.
- Viscosity can be measured using any number of viscometers or viscosity flow cups or can be compared by manually stirring with an ink knife or spatula and noting the viscosity difference.
- viscosity stability was assessed by measuring viscosity using a DIN 4 viscosity flow cup immediately after ink manufacture and then taking comparative viscosity readings after 24 hours at 25 °C. A rise in viscosity after manufacture is considered disadvantageous (see Table 5).
- the use of high acid value materials can present undesirable side effects such as a reduction in water/moisture barrier properties, discoloration and a reduction in printability performance.
- the novel adhesion promoters of the present invention exhibit improved stability and do not require the use of high acid value resins, thereby allowing simpler formulations with improved properties.
- present invention provides an adhesion promoter comprising: (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g.
- the adhesion promoter typically further comprises (c) one or more optional additives; and (d) a balance of volatile organic compound(s).
- the organotitanate compound is present in the adhesion promoter at a level of about 10 to 60% by weight.
- the polyamide is present in the adhesion promoter at a level of about 10 to 60%> by weight.
- the optional additive is present in the adhesion promoter at a level of up to about 20%> by weight.
- Component (d), the volatile organic compound is typically an organic solvent, such as an alcohol, ester or glycol solvent. In some systems water is more appropriate.
- the volatile organic solvent advantageously includes at least one alcohol solvent.
- the adhesion promoter may, for example, comprise: about 10 to 60 % by weight organotitanate compound; about 10 to 60 % by weight alcohol soluble polyamide having an acid and an amine value of from 1 to 25 mg KOH/g; and a balance of a solvent, which solvent includes an alcohol, optionally an ester and optionally a glycol.
- the adhesion promoting compound is typically suitable for use in liquid inks and coatings, especially liquid inks and coatings for flexible packaging.
- the present invention provides an ink or coating comprising an adhesion promoter comprising: (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g.
- the inks and coatings of the second aspect of the invention may, for example, comprise the adhesion promoting composition of the first aspect of the invention.
- the present invention provides the use of a combination of (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g to promote the adhesion of an ink or coating to a substrate.
- the combination used in the third aspect of the invention may, for example, be the adhesion promoter of the first aspect of the invention.
- a method of producing a printed or coated article comprising the step of applying the ink or coating comprising an adhesion promoter comprising: (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g to a substrate.
- the ink or coating applied in the method of the fourth aspect of the invention may, for example, be the ink or coating of the second aspect of the invention.
- the method may, optionally, further comprise the step of curing the ink or coating.
- a method of producing a laminated article comprising the steps of applying the ink or coating to a substrate and superimposing an overlay over the ink or coating to form a laminated article.
- a printed article comprising an ink or coating comprising a combination of (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g on a substrate.
- the ink or coating may, for example, be that of the second aspect of the invention.
- the printed article may, for example, be prepared in accordance with the method of the fourth aspect of the invention.
- the present invention offers novel adhesion promoters, which have been found to typically provide one or more of the following technical advantages over the prior art:
- Adhesion is observed on many coated plastic substrates, such as, but not limited to those coated with aluminum oxide, silica oxide, PVdC, acrylic, PVOH, nitrocellulose.
- Polyamides are used in ink and coating formulations to provide release characteristics to the printed package, preventing two packages adhering to one another.
- the adhesion promoter of the present invention has been found not only to be suitable for use on a broad range of substrates both in surface printing but has also been found to be useful as a lamination ink without adversely effecting the adhesion between layers.
- Figure 1 shows a printed article of the fifth aspect of the invention prepared according to the method of the fourth aspect of the invention including an ink or coating of the second aspect of the invention applied to a substrate.
- Figure 2 shows a laminated printed article of the fifth aspect of the invention prepared according to the fourth aspect of the invention in which an ink or coating of the second aspect of the invention is sandwiched between a substrate and an overlay.
- the present invention is directed to an adhesion promoter that is advantageously suitable for use in solvent-based liquid inks and coatings for flexible packaging, including non-direct food packaging that includes an organo -titanate with a synergistic polyamide additive.
- Component (a) the organo-titananium compound in the adhesion promoter of the first aspect of the invention is advantageously an organo-titanate selected from an titanium orthoester and an organo-titananium chelate.
- Titanium orthoesters are also referred to as esters of orthotitanic acid and are typically of the form Ti(OR) 4 wherein R is an alkyl, such as a Ci to Cs alkyl especially a C 3 to C 4 alkyl.
- the organo-titananium chelate are typically titanium (IV) chelates comprising one or more chelating ligands and, optionally, one or more alkoxy groups (-OR groups where R is alkyl as described above). Titanium (IV) forms chelates with a range of oxygen-containing compounds that include carboxylic acids, especially hydroxyl acids, for example, salicyclic acid and lactic acid; phosphoric acids and phosphate esters; polyols, for example, dihydroxy compounds; diketo compounds; hydroxy keto compounds; and amino alcohols.
- carboxylic acids especially hydroxyl acids, for example, salicyclic acid and lactic acid
- phosphoric acids and phosphate esters phosphoric acids and phosphate esters
- polyols for example, dihydroxy compounds; diketo compounds; hydroxy keto compounds; and amino alcohols.
- the organo-titananium compound is, for example, the reaction product of a titanium complex, such as a titanium orthoester, especially a titanium (IV) complex, and a phosphate ester or a ketone, such as a diketone or hydroxyl ketone.
- the organo-titananium compound may, for example, be a titanium phosphate compound.
- Suitable organo-titananium compounds include titanium diacetylacetonate, which is the reaction product of tetraisopropyltitanate and acetylacetone (2,4-pentanedione).
- Suitable phosphates include alkyl phosphates and amyl acid phosphates, especially alkyl phosphates.
- Suitable alkyl phosphates include monoalkyl phosphates, for example of the formula (R 1 0)PO(OH) 2 where R 1 is an alkyl group such as a Ci to Cio alkyl, especially a Ci to C 5 alkyl, and dialkylphosphates, for example of the formula (R 2 0)(R 3 0)PO(OH) where R 2 and R 3 are independently alkyl groups such as Ci to Cio alkyl, especially Ci to C 5 alkyl.
- Non- yellowing organo-titananium chelates are preferred such as, for example, titanium IV isopropoxide (such as that available under the trade name: Vertec RJCE).
- Organo-titananium chelates are especially preferred such as, for example, titanium butyl phosphate (such as those available under the trade names: Vertec IA-10, Borica Tytan API 00, Polygel LakeCM Ti-C 30, Dorf Ketal Tyzor IAM) and diisobutoxy-bisethylacetoaceto titanate (such as that available under the trade name: Dorf Ketal Tyzor IBAY).
- Organo -titanium chelates may also include a water-based titanium complex such as titanium lactic acid chelates, for example the chelate produced where two hydroxyl groups in Ti(OR) 4 are replaced by lactyl groups (such as that available under the tradename Dorf Ketal Tyzor LA).
- Organo-titananium chelates may be salts, such as the lactic acid titanium chelate ammonium salt, dihydroxy bis(ammonium lactato) titanium(IV).
- Component (b), the polyamide advantageously functions as a synergist that enhances the performance of the titanate adhesion promoter.
- the polyamide is typically a polyamide resin.
- the acid and amine value of the polyamide may, for example, be tested according to DIN 53 240.
- the polyamide typically has an acid value between 1 and 25 mg KOH/g, especially an acid value between about 3.5 and about 15 mg KOH/g.
- the polyamide advantageously has an acid value of at least 2.0 mg KOH/g, especially at least 3.0 mg KOH/g, for example at least 3.5 mg KOH/g.
- the polyamide has an acid value of at least 5.0 mg KOH/g, for example at least 7.0 mg KOH/g.
- the polyamide advantageously has an acid value of no more than 20 mg KOH/g, especially no more than 18 mg KOH/g, for example no more than 15 mg KOH/g.
- the polyamide typically has having an amine value between 1 and 25 mg KOH/g, especially an amine value between about 3.5 and about 15 mg KOH/g.
- the polyamide advantageously has an amine value of at least 2.0 mg KOH/g, especially at least 3.0 mg KOH/g, for example at least 3.5 mg KOH/g.
- the polyamide has an amine value of at least 5.0 mg KOH/g, for example at least 7.0 mg KOH/g.
- the polyamide advantageously has an amine value of no more than 20 mg KOH/g, especially no more than 18 mg KOH/g, for example no more than 15 mg KOH/g.
- Polyamide used in the ink industry are produced by condensation of dimerised fatty acids (manufactured by polymerizing tall oil fatty acids) and aliphatic diamines. Termination is determined by the ratio of dicarboxylic acid and diamine used in the preparation of the polyamide.
- the polyamide is typically the reaction product of a dicarboxylic acid and a diamine.
- the polyamide may, optionally, be the reaction product of from 1.2 to 1.0 mole equivalent of dicarboxylic acid with from 1.0 to 1.2 mole equivalent of diamine, especially the reaction product of from 1.1 to 1.0 mole equivalent of dicarboxylic acid with from 1.0 to 1.1 mole equivalent of diamine, especially the reaction product of from 1.05 to 1.0 mole equivalent of dicarboxylic acid with from 1.0 to 1.05 mole equivalent of diamine such as the reaction product of approximately a 1 : 1 ratio of dicarboxylic acid to diamine.
- the dimerised fatty acid is used in excess, for example 1.2 moles dimerised fatty acid to 1 mole aliphatic diamine an acid terminated polyamide is formed.
- the ratio is in favor of the aliphatic diamine for example 1 mole dimerised fatty acid to 1.2 moles aliphatic diamine an amine terminated polyamide is formed.
- an approximately equivalent ratio is used, i.e. 1 mole dimerised fatty acid to 1 moles aliphatic diamine a balanced polyamide with a balance of acid and amine functionality is formed.
- the polyamide of the adhesion promoter of the present invention is a balanced polyamide.
- Component (b), the polyamide is typically a co-solvent polyamide resin, an alcohol- reducible polyamide resin or an alcohol soluble polyamide resin, especially an alcohol soluble polyamide resin, for example a ethanol-soluble resin.
- the polyamides used in solvent-based liquid inks can be divided in three categories:
- Co-solvent polyamides designed to be soluble in blends of alcohols and/or aliphatic hydrocarbons. This class of resins is the least compatible with the solvency of flexographic printing inks and of most of the other modifying resins used in liquid inks.
- Alcohol-reducible polyamides designed to have co-solvent type properties, but to be alcohol-reducible; this gives an improved compatibility with modifying resins.
- Alcohol- soluble polyamides designed to be soluble in ethanol or in a blend of alcohols, and to also have a very good ester tolerance: this makes them the desirable polyamides to use in liquid inks, as alcohol and ester blends are the most common solvent-based solvency.
- Suitable polyamide resins for use in the adhesion promotion compound of the invention include, but are not limited to: Unirez 119; Unirez 138 Eurelon 975, Flexrez
- Component (d), the volatile organic diluent is typically an organic solvent, such as alcohol, ester or glycol solvent.
- the volatile organic solvent advantageously includes at least one alcohol.
- at least 40 wt% of the volatile organic diluent is alcohol, for example at least 50wt%, especially at least 60 wt% of the diluent.
- substantially all the volatile organic diluent is alcohol, for example at least 90wt%, such as 100%.
- the volatile organic diluent is an alcohol or a mixture of alcohols. Suitable alcohols include C-l to C-8 alcohols, especially C-l to C-8 aliphatic alcohol, for example C-l to C-8 alkyl alcohols.
- the alcohols may be straight chain, for example, ethanol (CH 3 -CH 2 -OH) or propan-l-ol (CH 3 (CH 2 ) 2 OH), branched, for example, 2-hydroxypropane (CH 3 -CH(OH)-CH 3 ) or cyclic such as cyclohexanol, especially straight chain or branched alicyclic alkyl alcohols.
- the alcohol solvents may include additional functional groups such as ester functionalities, for example, l-methoxy-2-propanol (C 4 Hio0 2 ) and 3-ethoxy-l- propanol (C 5 Hi 2 0 2 ).
- the ester solvents are typically C-l to C-8 esters, such as C-l to C-6 alkyl esters.
- the inks and coatings of the second aspect of the invention are advantageously liquid, for example, at 25 °C.
- the inks and coatings of the second aspect of the invention are preferably multipurpose inks and coating that are suitable for use both in surface printing and as lamination links.
- the inks and coating of the present invention are lamination inks that are, for example, suitable for use between plastics films in a laminated article.
- the adhesion promoter composition advantageously helps achieves the desired adhesion properties when incorporated into printing inks and coatings.
- the organotitanate compound and the polyamide of the adhesion promoter of the first aspect of the invention together comprise from about 0.5 to about 10% by weight (wt%) of the ink or coating of the second aspect of the invention, for example from about 0.5 to about 4 wt%.
- the adhesion promoter composition of the first aspect of the invention may, for example, be included in the liquid inks and coating of the second aspect of the invention at levels of from about 0.5 to about 10% by weight (wt%) of the ink or coatings, for example from about 1 to about 5 wt%. It has been found that using the adhesion promoters of the first aspect of the invention, good levels of adhesion of an ink or coating to a substrate can be obtained even when the organotitanate compound and the polyamide are present in the ink or coating at low levels. The low level of adhesion promoter use has been found not to substantially deleteriously effect the adhesion of subsequent layers of material to the printed or coated substrate when applied over the ink or coating.
- the printing inks and coatings of the second aspect of the invention are typically applied with dry coating weights of about 1 to about 10 g/m 2 (grams per square meter) and more preferably from about 2 to about 5 g/m 2 applied onto the plastic substrate by methods such as but not limited to gravure and flexography.
- the inks and coatings of the second aspect of the present invention are typically solvent-based, including water-based, formulations. It is also anticipated that the adhesion promoters of the present invention may also be suitable for use with other formulations including hybrid solvent-based / energy-curable inks or coatings as long as the adhesion promoter is compatible with the other materials contained in the formulation.
- the adhesion promoters When used in water-based or hybrid inks or coatings, typically comprise no more than 40 wt% volatile organic compound, for example no more than 20 wt%, especially no more than 10 wt% volatile organic compound.
- a solvent including water is typically included to provide a carrier for the polyamide.
- Ink and coatings formulations of the second aspect of the invention may contain any additives suitable for use in printing inks and coatings, such as, for example: waxes, plasticizers, biocides, extender pigments, surfactants, defoamers, stabilizers, silicones, etc.
- Ink and coatings formulations of the second aspect of the invention may be free of colorants, or may contain as an additive any organic or inorganic pigment or dye or special effect pigment (or combination thereof) that are suitable for use in printing inks or coatings.
- Additives suitable for use in printing inks and coating s, including those referred to above, may, optionally, be present in the adhesion promoter.
- component (c) the optional additive(s) is present in the adhesion promoter at a level of no more than about 20% by weight, for example no more than about 15 wt%.
- the optional additive(s) is present in the adhesion promoter at a level of no more than about 10 wt%, especially no more than about 5 wt5, for example no more than about 3 wt %.
- the adhesion promoter consist essentially of (a) the organotitanate compound, (b) the polyamide with the balance being a volatile organic diluent with substantially no additional components, for example, no more than 3 wt% additional components, especially no more than 2 wt% additional components.
- the present invention provides a method of improving the adhesion performance of an ink or coating comprising adding to said composition a combination of (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g.
- the present invention provides a method of improving the adhesion performance of an ink or coating comprising adding to said composition adhesion promoter of the first aspect of the invention.
- the combination of (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g may be used to improve the adhesion of an ink or coating to a flexible plastic film substrate.
- the combination may, advantageously, be used to promote adhesion of inks and coating that are used both in surface printing and as a lamination ink or coating.
- the composition may be used to improve the adhesion of a lamination ink or coating to a substrate.
- the use of the composition in a lamination ink or coating improves the adhesion of the overlay to the printed substrate of a laminate comprising said lamination ink between the layers of the laminate.
- the composition may be used in a lamination ink or coating to improve the bond strength of a laminate.
- the adhesion promoters of the present invention may, advantageously be used in lamination inks or coating.
- inks or coating comprising the adhesion promoter of the invention may be used in a method of preparing a laminated article comprising the steps of applying the ink or coating to a substrate, superimposing an overlay over the ink or coating on the substrate to form a laminated printed article.
- a method of producing a laminated printed article comprising the step of applying the ink or coating of the second aspect of the invention to a substrate and superimposing an overlay over the ink or coating on the substrate to form a laminated printed article.
- the method may, for example, involve a curing step in which the ink or coating is cured prior to the superimposing of the overlay.
- the overlay is typically a film of plastics material, especially a flexible plastics material.
- heat and/or pressure is applied to form the laminated article, for example to bond the substrate and the overlay together.
- the method of producing the printed article may include a lamination step, for example a step in which the coverlay on the substrate is heated and or pressure is applied to the overlay on the substrate.
- the heating typically involves heating to a temperature of about 100 °C or more, especially about 120 °C or more.
- an adhesive is additionally applied between the substrate and the overlay, for example, between the ink or coating and the overlay.
- the adhesive may be applied to the printed ink or coating on the substrate, either as a dry film or a liquid composition or may be applied to the overlay prior to the bringing together of the overlay and the printed substrate.
- Inks and coating of the present invention have been found to be suitable for use in lamination applications. The ink or coating advantageously remains adhered to the substrate and also enabling good lamination bond strengths to be achieved, for example by forming a strong bond to the adhesive.
- solvent-based liquid inks containing the novel adhesion promoter exhibit improved adhesion onto plastic substrates, with excellent rheo logical stability without adversely affecting other printing ink properties.
- the adhesion promoters of the present invention advantageously helps to achieve desired adhesion and resistance properties in inks and coatings, for example in solvent-based liquid inks and coatings, over a wide range of substrates, including traditionally difficult substrates such as, but not limited to, those substrates coated with aluminum oxide, silica oxide, PVdC, Acrylic, PVOH and Nitrocellulose. This makes the adhesion promoters of the present invention and highly desirable for use in liquid inks.
- the substrate may, for example be used in the formation of a flexible packaging, for example a flexible packaging used to package a foodstuff.
- the printed article is a flexible packaging.
- the novel adhesion promoters are advantageously stable in all colors and do not require the addition of stabilizing resins (such as high acid value resins) that are commonly required with titanate adhesion promoters, thereby simplifying formulations and overcoming common downsides of stabilizing resins.
- the present invention typically provides:
- An adhesion promoter comprising about 10-60% by weight organo -titanate compound, about 10-60% by weight polyamide having an acid and amine value between 1 and 25mg KOH/g and a volatile organic diluent, especially an alcohol.
- An adhesion promoter that allows harmonization of adhesion additives employed in printing ink formulations, allows lower amounts to be used to achieve the desired adhesion properties, and allows removal of stabilizing resins such as high acid value resins (all major benefits).
- RJCE titanium IV isopropoxide (Vertec RJCE)
- Flex-Rez 1084AS is a polyamide resin with an acid number of ⁇ 15 mgKOH/g and an amine number of ⁇ 15 mgKOH/g
- Uni-Rez 138 is a polyamide resin with an acid number of 1.6 mgKOH/g and an amine number of 2.1 mgKOH/g
- Casamid 874 is a polyamide resin with an acid number of ⁇ 6 mgKOH/g and an amine number of ⁇ 6 mgKOH/g
- Surkopak 5246 and Surkopak 5323 are a thermoplastic polyurethane resins supplied by BIP (Oldbury) Ltd.
- PU3552 is an elastomeric polyurethane resin supplied by Arakawa
- Neorez U-395 is an elastomeric polyurethane resin supplied by DSM
- ATBC is a citrate plasticizer supplied by Univar Ltd.
- TSDA is an ethanol solvent supplied by Brenntag
- Tyzor AA75 is a titanium diacetylacetonate adhesion promoter supplied by DorfKetal
- Vertec IA10 is a titanium butyl phosphate adhesion promoter supplied by Dorf Ketal.
- Coatosil 1770 is a silane adhesion promoter supplied by Momentive
- RDI-S is a Ti0 2 pigment supplied by Sachtleben
- OPP substrates are supplied as Mobil MB400 and Innovia RGP25
- Chem PET substrates are supplied as Dupont Teijin Mylar 813 and Hostaphan GN4600
- ALOx PET substrates are supplied as Amcor Camclear and Toray Barrialox
- PVdC PET substrates are supplied as Toray T22.00 and Dupont Teijin D887
- PVdC PET substrates are supplied as Mobil MB777 and Innovia RDU21
- OPA substrates are supplied as Sudpack OPA and Wipak OPA
- Table 3a White Ink Formulae for Discoloration Testing Note: The percentages and types of materials used in the Examples in Tables 2 and 3, represent typical ink formulations where the inventive adhesion promoters can be used. An ink formulator with skill in the art would know that the type and percent of materials could be altered for various end-use properties. Examples of other resins that could be substituted or added to the above formulations include vinyl' s, urethanes, acrylics, olefins, epoxies, emulsion resins; acrylated resins; or any other film forming material suitable for use in printing inks or coatings.
- the inventive adhesion promoters would be used in printing inks or coatings applied by flexographic or gravure printing processes, but it is understood that the adhesion promoters could also be used in inks or coatings used in other printing or application processes (e.g. litho, inkjet; screen, dip and spray applications; etc.) Adhesion
- Adhesion of printed liquid inks is measured by each of the three industry standard tests outlined below. Printed proofs are prepared using lab ink proofing equipment as described above, side by side other on the same substrate to ensure identical test conditions. Inks to be compared are always printed alongside each other. Tests are carried out immediately after printing and after a further 24 hours time period where the prints are maintained at room temperature: 25 °C.
- Tape Adhesion Industry accepted tape adhesion test was made using 1 inch wide red Scapa tape, ref # 1112 is applied over the printed surface and then peeled rapidly at an angle of 135°. Results are determined by the percentage ink remaining after the removal of the adhesive tape.
- the printed substrate is then observed for failure of the ink film (i.e. loss of adhesion) and assigned a number from 1 to 5, with 1 representing either very minimal or no loss due to adhesion/scratch/wrinkle failure, and 5 representing complete loss of adhesion/scratch/wrinkle.
- the average score from each of the three tests is provided in table 4 below. Generally speaking, a score of 1 or 2 is preferred, but 3 or 4 may be acceptable for certain end-use applications.
- Water/moisture barrier resistance is measured by placing the printed surface in the SATRA rub resistance tester using a water soaked felt pad under pressure with a 1.76 kg weight for 40 cycles at room temperature.
- the printed substrate is then observed for failure of the ink film (i.e. loss of adhesion) and assigned a number from 1 to 5, with 1 representing either very minimal or no adhesion loss, and 5 representing complete loss of adhesion.
- a score of 1 or 2 is preferred, but 3 or 4 may be acceptable for certain end-use applications.
- adhesion promoters currently employed in liquid inks for flexible packaging are known to cause discoloration, often seen as yellowing in white inks.
- Titanium acetyl acetone (among others) is an example of a class of adhesion promoters associated with yellowing.
- the adhesion promoters of the present invention exhibit significantly reduced discoloration, in some case eliminating discoloration all together.
- yellowing tests were carried out by substituting the comparative adhesion promoters for the inventive adhesion promoter in Example 4 (white ink). The ink is applied using a 140 lines per inch flexo hand anilox.
- a rating of 1 indicates minimal or no yellowing; a rating of 5 indicates severe yellowing. Generally speaking, a score of 1 or 2 is preferred, but 3, 4 or 5 may be acceptable for certain end-use applications. Odor
- the level of odor is assigned a number from 1 to 5, where 1 signifies no discemable odor and 5 signifies significant odor. Generally speaking, a score of 1 or 2 is preferred, but 3, 4 or 5 may be acceptable for certain end-use applications.
- the printed substrate is brought into contact with 0 the secondary substrate to which the adhesive has been applied to achieve a dry film weight of 1.3 to 4.0 gsm (grams per square meter) or as recommended by the adhesive supplier using an adhesive laminator.
- the laminate sandwich of substrate-ink- adhesive-substrate is left to cure at room temperature for at least 24 hours before testing.
- the cured laminate is cut into a 15 mm width which can be heat-sealed giving 5 an indication of bond strength in the heat seal area.
- the laminate is heat sealed at 140 °C, at 20 psi (140 kPa) pressure for a 1 second dwell time.
- the ends of the primary and secondary substrates are fixed to the jaws of the bond strength tester so as to form a T peel and then pulled apart.
- the force needed to carry out the de-lamination is recorded in Newtons/15 mm units along percentage ink transfer i.e.: 100% ink 0 transfer means ink peeling away from the printed substrate to the secondary substrate;
- 0% ink transfer means the adhesive remains on either the ink (primary) substrate or the secondary substrate. This is seen to be an advantageous ink property.
- FIG. 10 A first embodiment of a printed article of the fifth aspect of the invention is shown in Figure 1.
- the printed article (10) includes a printed image (1) of the cured an ink or coating of the second aspect of the invention superimposed on a substrate (2).
- the printed article (20) of the first embodiment has been prepared according to the method of the fourth aspect of the invention by applying an ink or coating comprising an adhesion promoter comprising: (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g to a substrate (2) and curing the ink or coating to provide a printed image (1).
- an adhesion promoter comprising: (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g to a substrate (2) and curing the ink or coating to provide a printed image (1).
- a second embodiment of a printed article of the fifth aspect of the invention is shown in Figure 2.
- the printed article (20) is a laminated article in which a printed image (1) of the cured ink or coating of the second aspect of the invention is sandwiched between a substrate (2) and an overlay (3).
- the laminated printed article (20) of the second embodiment has been prepared according to the method of the fourth aspect of the invention by applying an ink or coating comprising an adhesion promoter comprising: (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g to a substrate (2) and curing the ink or coating to provide a printed image (1), superimposing an overlay (3) on the printed image (1) and applying heat and pressure to form the laminated printed article (20).
- an adhesion promoter comprising: (a) organotitanate compound; (b) polyamide having an acid and an amine value of from 1 to 25 mg KOH/g to a substrate (2) and curing the ink or coating to provide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11755422.0A EP2611875B1 (en) | 2010-09-01 | 2011-09-01 | An adhesion promoting compound |
BR112013004855-7A BR112013004855B1 (en) | 2010-09-01 | 2011-09-01 | adhesion promoter of an ink or coating, ink or coating composition, method of producing a printed article and printed article |
ES11755422.0T ES2657228T3 (en) | 2010-09-01 | 2011-09-01 | An adhesion promotion compound |
US13/819,493 US9139716B2 (en) | 2010-09-01 | 2011-09-01 | Adhesion promoting compound |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US37914910P | 2010-09-01 | 2010-09-01 | |
US61/379,149 | 2010-09-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012028882A1 true WO2012028882A1 (en) | 2012-03-08 |
Family
ID=44645739
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2011/051641 WO2012028882A1 (en) | 2010-09-01 | 2011-09-01 | An adhesion promoting compound |
Country Status (5)
Country | Link |
---|---|
US (1) | US9139716B2 (en) |
EP (1) | EP2611875B1 (en) |
BR (1) | BR112013004855B1 (en) |
ES (1) | ES2657228T3 (en) |
WO (1) | WO2012028882A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015112528A1 (en) | 2014-01-22 | 2015-07-30 | Sun Chemical Corporation | Urethane-compatible polyester adhesion promoters |
CN113928035A (en) * | 2021-10-29 | 2022-01-14 | 浙江美浓世纪集团有限公司 | Gravure fission-simulating printing method |
WO2022216948A1 (en) | 2021-04-09 | 2022-10-13 | Lubrizol Advanced Materials, Inc. | Neutralized multi-amine dispersant compositions |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9956749B2 (en) * | 2014-01-13 | 2018-05-01 | Ford Global Technologies, Llc | Capacitive touch screen formed by injection compression molding |
US10266651B2 (en) * | 2014-12-18 | 2019-04-23 | Lubrizol Advanced Materials, Inc. | Water dispersible polyamide building blocks |
DE202015104179U1 (en) * | 2015-08-10 | 2015-08-17 | Hubergroup India Private Ltd. | Printing ink and printing varnish with excellent adhesion especially for food packaging |
EP3440139B1 (en) * | 2016-04-06 | 2021-01-13 | Sun Chemical Corporation | Multipurpose shrink sleeve printing ink |
US10259953B2 (en) | 2016-09-30 | 2019-04-16 | Borica Co., Ltd. | Adhesion promoted and ink composition |
DE102017001234B4 (en) * | 2017-02-03 | 2021-03-04 | Staedtler Mars Gmbh & Co. Kg | Use of a coating agent |
TWI841234B (en) | 2017-04-28 | 2024-05-01 | 美商盧伯利索先進材料有限公司 | Matted polyamide-pud |
CN107619599B (en) * | 2017-10-27 | 2020-11-13 | 上海金发科技发展有限公司 | Low-odor spraying-free polyamide composition and preparation method thereof |
JP6996259B2 (en) * | 2017-11-28 | 2022-01-17 | Dicグラフィックス株式会社 | Liquid ink composition |
WO2019139948A1 (en) | 2018-01-09 | 2019-07-18 | Sun Chemical Corporation | Group iv metal chelates and their use in radiation curable ink and coating compositions |
BR112020015346B1 (en) * | 2018-02-12 | 2021-10-26 | Sun Chemical Corporation | STAIN RESISTANT PAINT COMPOSITION |
EP3560709B1 (en) * | 2018-04-24 | 2020-08-12 | Rkw Se | Method for the manufacture of printed laminates of non-woven fabrics and film |
WO2020219029A1 (en) * | 2019-04-23 | 2020-10-29 | Bemis Company, Inc. | Process for producing adhesive-free laminates |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4087402A (en) | 1975-09-30 | 1978-05-02 | Kenrich Petrochemicals, Inc. | Organo-titanate chelates and their uses |
US4094853A (en) | 1975-05-15 | 1978-06-13 | Kenrich Petrochemicals, Inc. | Alkoxy titanate salts useful as coupling agents |
GB2161817A (en) * | 1984-07-20 | 1986-01-22 | Tioxide Group Plc | Compositions incorporating adhesion-promoting titanium compounds |
US4659848A (en) | 1984-07-20 | 1987-04-21 | Tioxide Group Plc | Titanium compositions |
US4725501A (en) | 1985-05-28 | 1988-02-16 | Ppg Industries, Inc. | Primer for adherence to plastic substrates |
US4909846A (en) | 1987-10-31 | 1990-03-20 | Huels Troisdorf Ag | Compositions based on titanium chelates of diols and titanium acylates |
US5116411A (en) | 1989-12-22 | 1992-05-26 | Topez Company | Printing ink |
EP0730014A1 (en) * | 1995-03-03 | 1996-09-04 | Videojet Systems International, Inc. | Ink jet ink which is rub resistant to alcohol |
WO2004053003A1 (en) | 2002-12-11 | 2004-06-24 | Johnson Matthey Plc | Adhesion promoting compound and composition incorporating same |
WO2005049662A1 (en) | 2003-11-17 | 2005-06-02 | Sun Chemical Corporation | Reactive hydroxylated and carboxylated polymers for use as adhesion promoters |
US7619021B2 (en) | 2004-04-05 | 2009-11-17 | Sun Chemical Corporation | Adhesion promoting compound |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3117534B2 (en) * | 1992-02-17 | 2000-12-18 | 花王株式会社 | Vehicle for printing ink |
DE19905394A1 (en) * | 1999-02-10 | 2000-08-17 | Basf Ag | Liquid crystalline mixture |
FI116318B (en) * | 2003-02-27 | 2005-10-31 | Avantone Oy | Printed TTI indicators |
-
2011
- 2011-09-01 US US13/819,493 patent/US9139716B2/en active Active
- 2011-09-01 EP EP11755422.0A patent/EP2611875B1/en active Active
- 2011-09-01 WO PCT/GB2011/051641 patent/WO2012028882A1/en active Application Filing
- 2011-09-01 BR BR112013004855-7A patent/BR112013004855B1/en active IP Right Grant
- 2011-09-01 ES ES11755422.0T patent/ES2657228T3/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4094853A (en) | 1975-05-15 | 1978-06-13 | Kenrich Petrochemicals, Inc. | Alkoxy titanate salts useful as coupling agents |
US4087402A (en) | 1975-09-30 | 1978-05-02 | Kenrich Petrochemicals, Inc. | Organo-titanate chelates and their uses |
GB2161817A (en) * | 1984-07-20 | 1986-01-22 | Tioxide Group Plc | Compositions incorporating adhesion-promoting titanium compounds |
US4659848A (en) | 1984-07-20 | 1987-04-21 | Tioxide Group Plc | Titanium compositions |
US4725501A (en) | 1985-05-28 | 1988-02-16 | Ppg Industries, Inc. | Primer for adherence to plastic substrates |
US4909846A (en) | 1987-10-31 | 1990-03-20 | Huels Troisdorf Ag | Compositions based on titanium chelates of diols and titanium acylates |
US5116411A (en) | 1989-12-22 | 1992-05-26 | Topez Company | Printing ink |
EP0730014A1 (en) * | 1995-03-03 | 1996-09-04 | Videojet Systems International, Inc. | Ink jet ink which is rub resistant to alcohol |
WO2004053003A1 (en) | 2002-12-11 | 2004-06-24 | Johnson Matthey Plc | Adhesion promoting compound and composition incorporating same |
WO2005049662A1 (en) | 2003-11-17 | 2005-06-02 | Sun Chemical Corporation | Reactive hydroxylated and carboxylated polymers for use as adhesion promoters |
US7619021B2 (en) | 2004-04-05 | 2009-11-17 | Sun Chemical Corporation | Adhesion promoting compound |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015112528A1 (en) | 2014-01-22 | 2015-07-30 | Sun Chemical Corporation | Urethane-compatible polyester adhesion promoters |
EP3097160A4 (en) * | 2014-01-22 | 2017-08-09 | Sun Chemical Corporation | Urethane-compatible polyester adhesion promoters |
US10851202B2 (en) | 2014-01-22 | 2020-12-01 | Sun Chemical Corporation | Urethane-compatible polyester adhesion promoters |
WO2022216948A1 (en) | 2021-04-09 | 2022-10-13 | Lubrizol Advanced Materials, Inc. | Neutralized multi-amine dispersant compositions |
CN113928035A (en) * | 2021-10-29 | 2022-01-14 | 浙江美浓世纪集团有限公司 | Gravure fission-simulating printing method |
Also Published As
Publication number | Publication date |
---|---|
EP2611875A1 (en) | 2013-07-10 |
US20130157020A1 (en) | 2013-06-20 |
US9139716B2 (en) | 2015-09-22 |
BR112013004855B1 (en) | 2020-12-22 |
ES2657228T3 (en) | 2018-03-02 |
EP2611875B1 (en) | 2017-11-08 |
BR112013004855A2 (en) | 2016-06-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9139716B2 (en) | Adhesion promoting compound | |
JP5926630B2 (en) | Liquid ink | |
US8268108B2 (en) | Gas barrier coating having improved bond strength | |
JP2010248466A (en) | Printing ink composition for laminate | |
EP3459990A1 (en) | Oxygen barrier coating composition | |
JP5487492B1 (en) | Printing ink laminate | |
JP6485092B2 (en) | Polyurethane urea resin composition for gravure or flexographic printing ink | |
JP2016150945A (en) | Polyurethaneurea resin composition for gravure or flexographic printing ink | |
EP3749722B1 (en) | Smear resistant ink composition | |
JP6194817B2 (en) | Printing ink composition | |
JP6256102B2 (en) | Printing ink composition | |
CA2013996A1 (en) | Water-based chemical compositions | |
JP6255123B1 (en) | Liquid ink composition | |
JP7082740B2 (en) | Liquid ink composition for front printing | |
WO2023146700A1 (en) | Adhesive for digital ink printed laminates | |
JP2019123823A (en) | Liquid printing ink composition for surface printing and printed matter | |
JP2019147889A (en) | Liquid ink composition for surface printing | |
JP2007314682A (en) | Ink composition having high luminance feeling and degradation-preventing capability for retort product | |
JP6256103B2 (en) | Printing ink composition | |
JP2019119823A (en) | Liquid printing ink composition for surface printing, and printed matter | |
JP2019006909A (en) | Liquid ink composition | |
JP6996259B2 (en) | Liquid ink composition | |
US20200198306A1 (en) | Flexible packaging lamination compositions and flexible packaging | |
JPH07103220B2 (en) | Binders for printing inks and overcoat varnishes | |
WO2005028533A1 (en) | Low molecular weight polyurethane resins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11755422 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13819493 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2011755422 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011755422 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112013004855 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112013004855 Country of ref document: BR Kind code of ref document: A2 Effective date: 20130228 |